[Au12 (SR)6 ]2- , As Smaller 8-Electron Gold Nanocluster Retaining an SP3 -Core. Evaluation of Bonding and Optical Properties from Relativistic DFT Calculations.

Exploring the versatility of atomically precise clusters is a relevant issue in the design of functional nanostructures. Superatomic clusters offer an ideal framework to gain further understanding of the different distinctive size-dependent physical and chemical properties. Here, we propose [Au12 (SR)6 ]2- as a minimal 8-electron superatom related to the prototypical [Au25 (SR)18 ]- cluster, depicting half of its core-mass (2.3 kDa vs 5.0 kDa). The [Au12 (SMe)6 ]2- cluster fulfills a 1S2 1P6 electronic configuration, with a distorted tetrahedral Au8 core further viewed as an SP3 -hybridized superatom. The distinctive optical properties show a blue-shift for the first relevant 1P→1D transition, in comparison to [Au25 (SR)18 ]- . In addition, chiroptical activity is observed, denoting intrinsic core chirality. We expect that our results can shed light into the variation of the molecular properties according to the size-dependent properties, and serve as guidelines for further experimental exploration of minimal or ultrasmall nanoclusters.